Ternary azeotropic-like compositions with 1,1,1,2,3,3-hexafluoro-3-methoxy-propane and 1-bromopropane

ABSTRACT

Ternary azeotrope and azeotrope-like compositions containing 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and a third component, and uses thereof, are described.

TECHNICAL FIELD

This invention relates to ternary azeotrope and azeotrope-likecompositions containing 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane and a third component, and methods of using azeotropesand azeotrope-like compositions to clean substrates, deposit coatings,transfer thermal energy, and lubricate working operations.

BACKGROUND

Chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), andhydrochlorocarbons (HCCs, e.g., 1,1,1-trichloroethane and carbontetrachloride) have been used in a wide variety of solvent applicationssuch as drying, cleaning (e.g., the removal of flux residues fromprinted circuit boards), and vapor degreasing. These materials have alsobeen used in refrigeration and heat-transfer processes. However, thephotolytic and homolytic reactivity at the chlorine-containing carbonsites has been shown to contribute to depletion of the earth's ozonelayer. Additionally, the long atmospheric lifetime of CFCs has beenlinked to global warming. As a result, there has been a world-widemovement to replace CFCs.

The characteristics sought in replacements, in addition to low ozonedepletion potential, typically have included boiling point rangessuitable for a variety of solvent cleaning applications, lowflammability, and low toxicity. For some applications, solventreplacements should also have the ability to dissolve bothhydrocarbon-based and fluorocarbon-based soils. In some embodiments,solvent replacements also have low toxicity, have no flash points (asmeasured by ASTM D3278-98 e-1, “Flash Point of Liquids by Small ScaleClosed-Cup Apparatus”), have acceptable stability, have shortatmospheric lifetimes, and have low global warming potentials.

Hydrofluoroethers (HFEs) have gained interest as replacements for CFCsand HCFCs. Generally, HFEs are chemically stable, have low toxicity, arenon-flammable, and are non-ozone depleting.

In some instances, HFEs can form azeotropes with one or more co-solventsto modify or enhance the solvent characteristics of the HFE. Manyazeotropes possess properties that make them useful solvents. Forexample, azeotropes have a constant boiling point that avoids boilingtemperature drift during processing and use. In addition, when anazeotrope is used as a solvent, the properties remain constant becausethe composition does not change during boiling or reflux. Azeotropesthat are used as solvents also can be recovered conveniently bydistillation.

SUMMARY

In some embodiments, it is desirable to provide azeotrope-likecompositions that have good solvent strength. In another aspect, in someembodiments, it is desirable to provide azeotrope-like compositions thathave low flammability. In yet another aspect, in some embodiments, it isdesirable to provide azeotrope-like compositions that are non-ozonedepleting, and/or have a relatively short atmospheric lifetime so thatthey do not significantly contribute to global warming (i.e.,azeotrope-like compositions that have low global warming potential).

Briefly, in one embodiment, the present invention provides ternaryazeotrope-like compositions comprising a blend of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and a thirdcomponent. The third component is selected from methanol, ethanol, andisopropanol. In some embodiments, the azeotrope-like compositionsfurther comprise a lubricious additive, and/or hydrofluoric acid.

In another embodiment, the present invention provides a coatingcomposition comprising an azeotrope-like composition and at least onecoating material soluble or dispersible in the azeotrope-likecomposition.

In yet another embodiment, the present invention provides a process fordepositing a coating on a surface comprising applying a coatingcomposition comprising an azeotrope-like composition to at least aportion of a surface, wherein the at least one coating material issoluble or dispersible in the azeotrope-like composition.

In yet another embodiment, the present invention provides a process forlubricating metal, cermet, or composite wherein said process uses alubricating fluid comprising an azeotrope-like composition of thepresent invention.

In yet another embodiment, the present invention provides a process forassisting in the removal of contaminants from the surface of a substratecomprising the steps of contacting the substrate with one or more of theazeotrope-like compositions according to the present invention until thecontaminants are dissolved, dispersed, or displaced in or by theazeotrope-like composition, and removing the azeotrope-like compositioncontaining the dissolved, dispersed or displaced contaminants from thesurface of the substrate.

In yet another embodiment, the present invention provides a process forheat transfer wherein one or more of the azeotrope-like compositionsaccording to the present invention is used as a heat-transfer fluid.

The above summary is not intended to describe each embodiment. Thedetails of one or more embodiments of this disclosure are also set forthin the description below. Other features, objects, and advantages willbe apparent from the description and from the claims.

BRIEF DESCRIPTION OF DRAWINGS

Embodiments of the present disclosure are illustrated by way of example,and not limitation, in the accompanying drawings in which:

FIG. 1 is a schematic diagram of boiling point versus percent componentB, illustrating an azeotrope and azeotrope-like region.

DETAILED DESCRIPTION

An azeotropic composition, or azeotrope, comprises a mixture of two ormore substances that behaves like a single substance in which the vaporproduced by partial evaporation of the liquid azeotropic composition atits boiling point has the same composition as the liquid.

Azeotropic compositions are constant boiling point mixtures that exhibiteither a maximum boiling point that is higher than, or a minimum boilingpoint that is lower than, each of the individual components To defineterminology, FIG. 1 will be used. Shown in FIG. 1 is a hypotheticalmixture B′. Mixture B′ comprises components A and B. Mixture B′ isplotted as boiling point versus percent component B and is representedas curve 151.

In FIG. 1, the boiling points of the individual components, A and B, are95° C., and 100° C., respectively. The azeotrope of mixture B′ isrepresented by 155. This azeotrope has a boiling point that is lowerthan both component A and B.

Azeotrope-like compositions boil at temperatures that are either aboveeach of the individual components or below the boiling point of the eachof the individual components. The azeotrope-like region of mixture B′ isrepresented by shaded area 153. The B′ compositions comprising betweengreater than 0% and 40% of component B are considered azeotrope-like andhave boiling points that are lower than both component A and B. As canbe seen in FIG. 1, the azeotrope composition is included in the range ofazeotrope-like compositions for a particular mixture of substances. Aternary azeotrope and azeotrope-like composition may similarly beplotted to produce a three-dimensional volume, like the area 153.

The azeotrope-like compositions comprise1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and a thirdcomponent, which is selected from methanol, ethanol, and isopropanol.The concentration of the three components may vary substantially fromthe corresponding azeotropic composition, and the magnitude of thispermissible variation depends upon the specific third component. In someembodiments, the azeotropic-like composition comprises essentially thesame concentrations of the 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and a third component, as comprise the azeotrope formedbetween them at ambient pressure. In some embodiments, theazeotrope-like compositions exhibit no significant change in the solventpower of the composition over time.

Typically, azeotrope-like compositions retain some of the properties ofthe individual component solvents, which can enhance performance overthe individual components because of the combined properties.

In addition to the 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and a third component, other compounds that do notinterfere in the formation of the azeotrope-like composition may beadded. Typically, the other compounds will be present in small amounts.For example, in some embodiments, co-solvents or surfactants may bepresent to, for example, improve the dispersibility or the solubility ofmaterials, such as water, soils, or coating materials (e.g.,perfluoropolyether lubricants and fluoropolymers), in an azeotrope-likecomposition. In some embodiments, small amounts of lubricious additivesmay be present to, for example, enhance the lubricating properties of anazeotrope-like composition.

In some embodiments, the azeotrope-like compositions comprise a blend of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and a thirdcomponent, wherein the composition is selected from:

-   -   (i) a blend consisting essentially of        1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and        methanol, when fractionally distilled, forms a distillate        fraction that is an azeotrope consisting essentially of about        73.2 weight percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,        18.6 weight percent of 1-bromopropane and 8.2 weight percent of        methanol that boils about 45.3° C. at 732 torr; or    -   (ii) a blend consisting essentially of        1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and        ethanol, when fractionally distilled, forms a distillate        fraction that is an azeotrope consisting essentially of about        77.0 weight percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,        18.0 weight percent of 1-bromopropane and 5.0 weight percent of        ethanol that boils about 50.9° C. at 735 torr; or    -   (iii) a blend consisting essentially of        1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and        isopropanol when fractionally distilled, forms a distillate        fraction that is an azeotrope consisting essentially of about        79.9 weight percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,        17.6 weight percent of 1-bromopropane and 2.5 weight percent of        isopropanol that boils about 51.9° C. at 738 torr.

In some embodiments the concentrations of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and the thirdcomponent in the azeotrope-like composition differ from theconcentrations of such components in the corresponding azeotrope by nomore than about ten percent. In another embodiment, the concentrationsof 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and thethird component in the azeotrope-like composition differ from theconcentrations of such components in the corresponding azeotrope by nomore than about five percent.

In other words, the azeotrope-like composition may consist essentiallyof a blend of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane,and the third component wherein the concentrations differs from that ofthe azeotrope by +/−10 percent.:

-   -   (i) a blend consisting essentially of 65.9 to 80.5 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.7 to        20.5 weight percent of 1-bromopropane and 7.4 to 9.0 weight        percent of methanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        45.3° C. at 732 torr; or    -   (ii) a blend consisting essentially of 69.3 to 84.7 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.2 to        19.8 weight percent of 1-bromopropane and 4.5 to 5.5 weight        percent of ethanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        50.9° C. at 735 torr; or    -   (iii) a blend consisting essentially of 71.9 to 87.9 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 15.8 to        19.4 weight percent of 1-bromopropane and 2.3 to 2.8 weight        percent of isopropanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        51.9° C. at 738 torr.

In another embodiments, the azeotrope-like composition may consistessentially of a blend of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and the third component wherein the concentrationsdiffers from that of the azeotrope by +/−5 percent.:

-   -   (i) a blend consisting essentially of 69.5 to 76.9 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 17.7 to        19.5 weight percent of 1-bromopropane and 7.8 to 8.6 weight        percent of methanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        45.3° C. at 732 torr; or    -   (ii) a blend consisting essentially of 73.2 to 80.8 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 17.1 to        18.9 weight percent of 1-bromopropane and 4.8 to 5.2 weight        percent of ethanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        50.9° C. at 735 torr; or    -   (iii) a blend consisting essentially of 75.9 to 83.9 weight        percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.7 to        18.4 weight percent of 1-bromopropane and 2.4 to 2.6 weight        percent of isopropanol, when fractionally distilled, forms a        distillate fraction that is an azeotrope that boils about        51.9° C. at 738 torr.

As is known in the art, the composition of the azeotrope will vary withpressure, e.g., as the ambient pressure increases, the boiling point ofa liquid increases, and similarly, as the ambient pressure decreases,the boiling point of a liquid decreases. In some embodiments, theazeotrope-like compositions are homogeneous; i.e., they form a singlephase under ambient conditions (i.e., at room temperature andatmospheric pressure).

The azeotrope-like compositions can be prepared by mixing the desiredamounts of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, andthe third component, and any other minor components (e.g., surfactantsor lubricious additives) together using conventional mixing means.

In some embodiments, the azeotrope-like compositions may be used incleaning processes, in heat-transfer processes, as a refrigerant, as alubricating fluid, as a coating liquid, and the like.

Various different solvent cleaning and/or decontamination techniques areknown in the art. In one embodiment, a cleaning process can be carriedout by contacting a contaminated substrate with one of theazeotrope-like compositions of this disclosure until the contaminants onthe substrate are substantially dissolved, dispersed, or displaced in orby the azeotrope-like composition, and then removing (for example, byrinsing the substrate with fresh, uncontaminated azeotrope-likecomposition or by removing a substrate immersed in an azeotrope-likecomposition from a bath and permitting the contaminated azeotrope-likecomposition to flow off of the substrate) the azeotrope-like compositioncontaining the dissolved, dispersed, or displaced contaminant from thesubstrate. The azeotrope-like composition can be used in either thevapor or the liquid state (or both), and any of the known techniques for“contacting” a substrate can be used. For example, the liquidazeotrope-like composition can be sprayed or brushed onto the substrate,the vaporous azeotrope-like composition can be blown across thesubstrate, or the substrate can be immersed in either a vaporous or aliquid azeotrope-like composition. In some embodiments, elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning.

In some embodiments, the azeotrope-like compositions are also useful forremoving contamination during semiconductor fabrication. For example, anintegrated circuit or other small component may be exposed to theazeotrope-like composition to remove material not wanted on a surface,including photoresist residue, post-ion implant residue, post-etchresidue, particulates, and even water.

In some embodiments, exemplary processes of this disclosure can be usedto clean organic and/or inorganic substrates. Representative examples ofsubstrates include: metals; ceramics; glass; silicon wafers; polymersfor example polycarbonate, polystyrene, andacrylonitrile-butadiene-styrene copolymer; natural fibers (and fabricsderived there from) for example, cotton, silk, linen, wool, ramie, fur,leather, and suede; synthetic fibers (and fabrics derived therefrom) forexample, polyester, rayon, acrylics, nylon, polyolefin, acetates,triacetates, and blends thereof; fabrics comprising natural andsynthetic fibers; and combinations (e.g., laminates, mixtures, blends,etc.) of the foregoing materials. In some embodiments, the process isespecially useful in the precision cleaning of electronic components(e.g., circuit boards); optical or magnetic media; and medical devicesand medical articles for example syringes, surgical equipment,implantable devices, and prosthesis.

In some embodiments, exemplary cleaning and/or decontamination processescan be used to dissolve or remove most contaminants from the surface ofa substrate. For example, materials such as light hydrocarboncontaminants; higher molecular weight hydrocarbon contaminants such asmineral oils, greases, cutting and stamping oils and waxes; fluorocarboncontaminants such as perfluoropolyethers, bromotrifluoroethyleneoligomers (gyroscope fluids), and chlorotrifluoroethylene oligomers(hydraulic fluids, lubricants); silicone oils and greases; photoresist,solder fluxes; particulates; and other contaminants encountered inprecision, electronic, metal, and medical device cleaning can beremoved. In some embodiments, the process is particularly useful for theremoval of hydrocarbon contaminants (especially, light hydrocarbonoils), fluorocarbon contaminants, photoresist and particulates.

In some embodiments, the azeotrope-like compositions are also useful forextraction. Here, cleaning involves removing contaminants (e.g., fats,waxes, oils, or other solvents) by dissolution or displacement of thesematerials from substances (e.g., naturally occurring materials, foods,cosmetics, and pharmaceuticals).

In some embodiments, exemplary azeotrope-like compositions can also beused in coating deposition applications, where the azeotrope-likecomposition functions as a carrier for a coating material to enabledeposition of the material on the surface of a substrate, thus providinga coating composition comprising the azeotrope-like composition and aprocess for depositing a coating on a substrate surface using theazeotrope-like composition. The process comprises the step of applyingto at least a portion of at least one surface of a substrate a coatingof a liquid coating composition comprising (a) an azeotrope-likecomposition; and (b) at least one coating material that is soluble ordispersible in the azeotrope-like composition. The coating compositioncan further comprise one or more additives (e.g., surfactants, coloringagents, stabilizers, anti-oxidants, flame retardants, and the like).Preferably, the process further comprises the step of removing theazeotrope-like composition from the deposited coating by, e.g., allowingevaporation (which can be aided by the application of, e.g., heat orvacuum).

The coating materials that can be deposited by the process include:pigments, silicone lubricious additives, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, cosmetics, releaseagents, inorganic oxides, and the like, and combinations thereof.Preferred materials include: perfluoropolyethers, hydrocarbons, andsilicone lubricious additives; amorphous copolymers oftetrafluoroethylene; polytetrafluoroethylene; and combinations thereof.Representative examples of materials suitable for use in the processinclude: titanium dioxide, iron oxides, magnesium oxide,perfluoropolyethers, polysiloxanes, stearic acid, acrylic adhesives,polytetrafluoroethylene, amorphous copolymers of tetrafluoroethylene,and combinations thereof. Any of the substrates described above (fordecontamination applications) can be coated. Particularly useful in oneembodiment, is coating magnetic hard disks or electrical connectors withperfluoropolyether lubricants or medical devices with siliconelubricious additives.

To form a coating composition, the components of the composition (i.e.,the azeotrope-like composition, the coating material(s), and anyadditive(s) used) can be combined by any conventional mixing techniqueused for dissolving, dispersing, or emulsifying coating materials, e.g.,by mechanical agitation, ultrasonic agitation, manual agitation, and thelike. The azeotrope-like composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. In some embodiments, the coating material(s) comprise fromabout 0.1 to about 10 weight percent of the coating composition.

Exemplary deposition processes of this disclosure can be carried out byapplying the coating composition to a substrate by any conventionaltechnique. For example, the composition can be brushed or sprayed (e.g.,as an aerosol) onto the substrate, or the substrate can be spin-coated.In some embodiments, the substrate is coated by immersion in thecomposition. Immersion can be carried out at any suitable temperatureand can be maintained for any convenient length of time. If thesubstrate is a tube, such as a catheter and it is desired to ensure thatthe composition coats the lumen wall of the catheter, it may beadvantageous to draw the composition into the lumen by the applicationof reduced pressure.

In some embodiments, after a coating is applied to a substrate, theazeotrope-like composition can be removed from the deposited coating byevaporation. In some embodiments, the rate of evaporation can beaccelerated by application of reduced pressure or mild heat. The coatingcan be of any desired thickness. Generally, the thickness will bedetermined by, for example, such factors as the viscosity of the coatingmaterial, the temperature at which the coating is applied, and the rateof withdrawal (if immersion is used).

In some embodiments, the azeotrope-like compositions of the presentinvention can be used as heat-transfer fluids in heat-transfer processeswhere the heat-transfer fluids can transfer thermal energy (e.g., heat)either in a direct or indirect manner. Direct heat transfer (sometimescalled “direct contact heat transfer”) refers to a heat-transfer processwherein a heat-transfer fluid conducts heat directly to and/or from aheat sink or source to a fluid by directly contacting the fluid with theheat sink or source. Examples of direct heat transfer include theimmersion cooling of electrical components and the cooling of aninternal combustion engine.

Indirect heat transfer refers to a heat-transfer process wherein aheat-transfer fluid conducts heat to and/or from a heat sink or sourcewithout directly contacting the fluid with the heat sink or source.Examples of indirect heat transfer include: refrigeration, airconditioning and/or heating (e.g., using heat pumps) processes, such asare used in buildings, vehicles, and stationary machinery. In otherembodiments, a process for transferring heat is provided comprisingemploying an azeotrope-like composition as a secondary loop refrigerantor as a primary loop refrigerant. In these embodiments, the secondaryloop refrigerant (i.e., a wide temperature range liquid fluid) providesa means for transferring heat between the heat source and the primaryloop refrigerant (i.e., a low temperature-boiling fluid, which acceptsheat by e.g., expanding to a gas and rejects heat by being condensed toa liquid, typically by using a compressor). Examples of equipment inwhich the azeotrope-like composition may be useful include: centrifugalchillers, household refrigerator/freezers, automotive air conditioners,refrigerated transport vehicles, heat pumps, supermarket food coolersand display cases, and cold storage warehouses.

In indirect heat-transfer processes, lubricious additives for heattransfer can be incorporated in the heat-transfer fluid where movingparts (e.g., pumps and valves) are involved to ensure that the movingparts continue to work over long periods of time. Generally, theselubricious additives should possess good thermal and hydrolyticstability and should exhibit at least partial solubility in theheat-transfer fluid. Examples of suitable lubricious additives include:mineral oils, fatty esters, highly halogenated oils such aschlorotrifluoroethylene-containing polymers, and synthetic lubriciousadditives such as alkylene oxide polymers. The azeotrope-likecompositions can also function as a working fluid in an organic Rankinecycle, for example to recover energy from sources such as waste heatfrom industrial processes, geothermal heat, or solar heat.

In some embodiments, the azeotrope-like compositions can be used toformulate working fluids or lubricants that comprise the azeotrope-likecompositions of the present invention and at least one fully volatilelubricious additive. A lubricious additive is defined herein as anadditive that modifies the coefficient of friction between a work pieceand tooling. In some embodiments, an azeotrope-like composition with thelubricious additive form the working fluid for a working operation.

Exemplary substrates in working operations include: metal, cermet, andcomposite work pieces. Exemplary metals include: refractory metals(e.g., tantalum, niobium, molybdenum, vanadium, tungsten, hafnium,rhenium, and titanium); precious metals (e.g., silver, gold, andplatinum); high temperature metals (e.g., nickel, titanium alloys, andnickel chromes); other metals including, for example, magnesium, copper,aluminum, steel (e.g., stainless steels); alloys (e.g., brass, andbronze); and any combinations thereof.

Typically, working fluids lubricate machining surfaces, resulting in asmooth and substantially residue-free machined work piece surface. Insome embodiments, exemplary working fluids used in these operations alsocool the machining environment (e.g., the surface interface between awork piece and a machining tool) by, for example, removing heat and/orparticulate matter therefrom.

Cermets are semi synthetic-products consisting of a mixture of ceramicand metallic components having physical properties not found solely ineither one alone. Examples include: metal carbides, oxides, andsilicides.

Composites are described herein as combinations (e.g., laminate,mixture, blend, etc.) of high temperature fibers in a polymer matrix,for example, a glass or carbon fiber in an epoxy resin.

In some embodiments, a working fluid is formulated so that the cuttingand forming processes are lubricated to reduce friction, heat build-upin the tool or work piece, and/or prevent material transfer from thework piece to the tool. In some embodiments, a working fluid fully wetsthe working tooling. In some embodiments, the azeotrope-like compositionincluded in the working liquid evaporates from the working tool and workpiece. In some embodiments, the lubricious additive is present as a thinfilm that reduces friction and heat build-up on the surfaces of the tooland work piece, and/or prevents material transfer from the work piece tothe tooling. Generally, the lubricious additive is selected such that itis sufficiently high in boiling point to lubricate the working processwithout evaporating prematurely and still low enough in boiling point tofully evaporate from the working process so that little or no residueremains (i.e., is volatile). Examples of lubricious additives forworking operations include: esters of C₈ to C₁₄ fatty acids, alkyleneglycol ethers, hydrocarbon distillates, and esters of lactic acid.

In each of the described uses, the azeotrope-like composition can beused as such, or a blend of azeotrope-like compositions may be used,provided the blend also is azeotrope-like. Similarly, minor amounts ofco-solvents can be added to the azeotrope-like compositions, providedthe addition does not disrupt the azeotropic behavior. Usefulco-solvents may include, for example, hydrofluorocarbons (HFCs),hydrocarbons, hydrochlorocarbons (HCCs), or water. Representativeexamples of suitable co-solvents include: carbon dioxide;1,1-difluoroethane; 1-hydropentadecafluoroheptane;1,1,1,2-tetrafluoroethane; 1,1,1,3,3-pentafluoropropane;2-chloropropane; water; saturated perfluorochemicals (e.g.,perfluoropentane, perfluorohexane, and perfluoro(N-methylmorpholine));and combinations thereof. In some embodiments, the azeotrope-likecomposition may further comprise hydrofluoric acid (HF).

Advantages and embodiments of this disclosure are further illustrated bythe following examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. All materialsare commercially available or known to those skilled in the art unlessotherwise stated or apparent.

EXAMPLES

The preparation, identification, and testing of the azeotrope-likecompositions of this disclosure are further described in the followingexamples. The particular materials and amounts thereof recited in theseexamples, as well as other conditions and details, should not beconstrued to unduly limit this invention. In these examples, allpercentages, proportions and ratios are by weight unless otherwiseindicated.

The 1,1,1,2,3,3-hexafluoro-3-methoxy-propane may be obtained fromSynquest Labs, Inc, Alachua, Fla., 1-bromopropane, and the thirdcomponent were obtained from Aldrich Chemical Company, Inc. (Milwaukee,Wis.).

Examples 1-3

Various mixtures of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and the third component were distilled at ambientpressure (732 to 738 torr) using the following procedure to identifywhether the mixture formed ternary azeotropes, and if so, thecomposition and boiling point (bp ° C.) of the azeotrope was recorded.At least two distillations were run and the results averaged. Themixtures were prepared and distilled at ambient lab pressure (726 to 732torr) in a concentric tube distillation column (Model 933 from AceGlass, Vinland, N.J.). In each case, the distillation was allowed toequilibrate at total reflux for at least 60 minutes. For eachdistillation, five successive distillate samples, each approximately 10percent by volume of the total liquid charge, were taken while operatingthe column at a liquid reflux ratio of 10 to 1. The compositions of thedistillate samples were then analyzed using an HP-5890 Series II PlusGas Chromatograph with an RTX-200 capillary column (Restek Corp.,Bellefonte, Pa.) or Nukol capillary column (Supelco, Bellefonte, Pa.) ora Quadrex 007 Series Methyl Silicone capillary column (Quadrex Corp.,New Haven, Conn.) and a thermal conductivity detector. The boiling pointof each distillate was measured using a thermocouple. Following thistest procedure, azeotropes of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and the third component were identified.

In Table 1 shown below, the compositions and boiling points (at theindicated pressure) of the three azeotropes are presented as Examples1-3.

TABLE 1 Exam- bp Pressure ple Composition (° C.) torr (kPa) 1 73.2%1,1,1,2,3,3-hexafluoro-3-methoxy- 45.3 732 (97.6) propane 18.6%1-bromopropane 8.2% methanol 2 77.0% 1,1,1,2,3,3-hexafluoro-3-methoxy-50.9 735 (98.0) propane 18.0% 1-bromopropane 5.0% ethanol 3 79.9%1,1,1,2,3,3-hexafluoro-3-methoxy- 51.9 738 (98.4) propane 17.6%1-bromopropane 2.5% isopropanol

Foreseeable modifications and alterations of this disclosure will beapparent to those skilled in the art without departing from the scopeand spirit of this disclosure. This invention should not be restrictedto the embodiments that are set forth in this application forillustrative purposes.

1. An azeotrope-like composition comprising a blend of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and a thirdcomponent, wherein the composition is selected from: (i) a blendconsisting essentially of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane and methanol, when fractionally distilled, forms adistillate fraction that is an azeotrope consisting essentially of about73.2 weight percent of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 18.6weight percent of 1-bromopropane and 8.2 weight percent of methanol thatboils about 45.3° C. at 732 torr; or (ii) a blend consisting essentiallyof 1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and ethanol,when fractionally distilled, forms a distillate fraction that is anazeotrope consisting essentially of about 77.0 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 18.0 weight percent of1-bromopropane and 5.0 weight percent of ethanol that boils about 50.9°C. at 735 torr; or (iii) a blend consisting essentially of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and isopropanolwhen fractionally distilled, forms a distillate fraction that is anazeotrope consisting essentially of about 79.9 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 17.6 weight percent of1-bromopropane and 2.5 weight percent of isopropanol that boils about51.9° C. at 738 torr.
 2. The azeotrope-like composition of claim 1wherein the concentrations of 1,1,1,2,3,3-hexafluoro-3-methoxy-propane,1-bromopropane, and the third component in the azeotrope-likecomposition differ from the concentrations of such components in thecorresponding azeotrope by no more than about ten percent.
 3. Anazeotrope-like composition according to claim 1 wherein theconcentrations of the ether and the organic solvent in theazeotrope-like composition differ from the concentrations of suchcomponents in the corresponding azeotrope by no more than about fivepercent.
 4. An azeotrope-like composition according to claim 1 whereinthe azeotrope-like composition is an azeotrope.
 5. The azeotrope-likecomposition of claim 1 comprising a blend of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane and a thirdcomponent, wherein the blend is selected from: (i) a blend consistingessentially of 65.9 to 80.5 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.7 to 20.5 weight percent of1-bromopropane and 7.4 to 9.0 weight percent of methanol; or (ii) ablend consisting essentially of 69.3 to 84.7 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.2 to 19.8 weight percent of1-bromopropane and 4.5 to 5.5 weight percent of ethanol; or (iii) ablend consisting essentially of 71.9 to 87.9 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 15.8 to 19.4 weight percent of1-bromopropane and 2.3 to 2.8 weight percent of isopropanol.
 6. Theazeotrope-like composition of claim 1 a blend of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 1-bromopropane, and a thirdcomponent wherein the blend is selected from: (i) a blend consistingessentially of 69.5 to 76.9 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 17.7 to 19.5 weight percent of1-bromopropane and 7.8 to 8.6 weight percent of methanol; or (ii) ablend consisting essentially of 73.2 to 80.8 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 17.1 to 18.9 weight percent of1-bromopropane and 4.8 to 5.2 weight percent of ethanol; or (iii) ablend consisting essentially of 75.9 to 83.9 weight percent of1,1,1,2,3,3-hexafluoro-3-methoxy-propane, 16.7 to 18.4 weight percent of1-bromopropane and 2.4 to 2.6 weight percent of isopropanol.
 7. Acoating composition comprising an azeotrope-like composition accordingto claim 1 and at least one coating material.
 8. A coated articlecomprising a substrate having a first surface, wherein the coatingcomposition of claim 7 contacts at least a portion of the first surface.9. A process for depositing a coating on a substrate surface comprisingapplying the coating composition of claim 7 to at least a portion of atleast one surface of the substrate, wherein the at least one coatingmaterial is soluble or dispersible in the azeotrope-like composition.10. A working fluid comprising the azeotrope-like composition accordingto claim 1 and a lubricious additive.
 11. The working fluid according toclaim 10, wherein said lubricious additive is volatile.
 12. Theazeotrope-like composition of claim 1, further comprising hydrofluoricacid.
 13. A process for lubricating metal, cermet, or composite, whereinsaid process is lubricated using the working fluid of claim
 10. 14. Aprocess for removing contaminants from the surface of a substratecomprising the steps of contacting the substrate with one or more of theazeotrope-like compositions according to claim 1 until the contaminantsare dissolved, dispersed, or displaced in or by the azeotrope-likecomposition, and removing the azeotrope-like composition containing thedissolved, dispersed or displaced contaminants from the surface of thesubstrate.
 15. A process for heat transfer wherein at least one of theazeotrope-like compositions according to claim 1 is used as aheat-transfer fluid.